Journal of Organic Chemistry p. 3140 - 3147 (1993)
Update date:2022-08-04
Topics:
Wade, Peter A.
Kondracki, Paul A.
1,1-Cyclopropanedimethanol dimethanesulfonate (1a) and the corresponding ditosylate 1b underwent thermal rearrangement at 110-140 deg C after melting.Short reaction time resulted in the formation of mixtures containing 1-(sulfonyloxy)cyclobutanemethanol sulfonates 5a,b (major), starting material, and 2-methylene-1,4-butanediol disulfonates 6a,b.Longer reaction times afforded complete conversion to disulfonates 6a,b, isolated in 49 and 62 percent yield, respectively.These reactions are postulated to proceed via initial carbocation formation, presumably interconverting bicyclobutonium and cyclopropylcarbinyl cations, which exist as ion pairs in the melt.Crossover experiments with dimesylate 1a and ditosylate 1b offer support for the presence of ion pairs in the melt: internal return competed with external trapping of the intermediate cations.Reaction of 1a and 2-methylene-1,4-butanediol ditosylate (6b) gave a mixture in which 2-methylene-1,4-butanediol 1-mesylate 4-tosylate (8) predominated over the isomeric 4-mesylate 1-tosylate 7 by a 5:1 ratio.Crossover experiments with 6a and 6b indicated that partial allylic substitution was occurring for the open-chain products under the thermolysis conditions.Reaction of 1a with excess tetrabutylammonium tosylate at 114-15 deg C afforded mixed 1-(sulfonyloxy)cyclobutanemethanol sulfonates and 2-methylene-1,4-butanediol disulfonates formed competitively by internal return and tosylate interception.Acetolysis of 1a at 42-43 deg C afforded predominately products of internal return early on the reaction profile.Longer reaction times afforded predominately monoacetates while reactions run at 108-10 deg C afforded substantial amounts of diacetates.Acetolysis of 1-acetoxycyclobutanemethanol mesylate (12a) resulted in the substitution of the mesyloxy group with substantial rearrangement.
View MoreHangzhou Hysen Pharma co.,Ltd.
website:http://www.hysenpharma.cn/
Contact:0086-571-88298791
Address:#701,Gudun Road Hangzhou
Compro Shijiazhuang Fine Chemical Co., Ltd
Contact:0086-311-89689838
Address:Economic and Technological Development Zone of Shijiazhuang,Hebei
jiangsu haian chemical co.,ltd.
Contact:86-513-15851283853
Address:No.99,Changjiang West Road,Haian County,Jiangsu Province,China
Nanjing Chemlin Chemical Co., Ltd.
website:http://www.echemlin.cn
Contact:+86-25-83697070
Address:Rm.902 Longyin Plaza, No. 217 Zhongshan Rd.(N) Nanjing 210009,China
Contact:+86-511-88790000
Address:338 North Yushan Rd, Zhenjiang, Jiangsu 212016
Doi:10.1246/cl.1993.469
(1993)Doi:10.1055/s-2002-19779
(2002)Doi:10.1016/S0957-4166(00)82331-9
(1993)Doi:10.1016/j.poly.2009.10.008
(2010)Doi:10.1134/S1070427211100132
(2011)Doi:10.1039/a808860h
(1999)